CN113150293B - Preparation method of two-dimensional nano-porous structure Pd-COF material - Google Patents
Preparation method of two-dimensional nano-porous structure Pd-COF material Download PDFInfo
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F2305/10—Photocatalysts
Abstract
The invention discloses a preparation method of a Pd-COF material with a two-dimensional nano-porous structure, which comprises the following steps: step 1, preparing an organic framework material COF by using 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine as raw materials and adopting a gradient thermal polycondensation method; step 2, use Pd (OAC)2And modifying an organic framework material COF as a Pd source to obtain the Pd-COF material with the two-dimensional nano-porous structure. The invention has mild reaction condition and simple and easily realized synthesis process, and takes Pd (OAC)2The Pd source is used for carrying out structural modification on an organic framework material COF, so that the photocatalytic decomposition efficiency of the COF on organic dyes and antibiotics is effectively improved, and the covalent organic framework material Pd-COF with a new ligand structure is successfully obtained.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a preparation method of a Pd-COF material with a two-dimensional nano porous structure.
Background
With the abuse of human antibiotics and the increasing amount of wastewater discharged in pharmaceutical technology, the residue of undegraded antibiotics in water environment is becoming one of the important factors which seriously affect human health and aquatic organism resources in the world. Therefore, the search for new materials that are novel, environmentally friendly and capable of significantly eliminating organic pollution is one of the major scientific problems that people need to solve at present. The solar-driven photocatalyst can convert solar energy into chemical energy and electric energy, and is proved to be an effective organic pollutant scavenger.
A covalent organic framework COF is a new research field which is rapidly developed in recent years, is a novel high-molecular material which is constructed by connecting light elements (C, H, B, N, O, Si and the like) through strong covalent bonds and is formed by reversible polymerization under thermodynamic control, and has wide application prospects in the aspects of clean energy application, catalysis, sensing and the like. Due to the charge transport performance of the pi electrons of the COF in a conjugate plane and in an axial direction, the COF has high carrier mobility, potential high-efficiency light capturing performance and electron transport capability. Therefore, COF materials are becoming hot of research in the field of catalysis. Compared with common semiconductor materials, COF materials can be designed into a wide variety of porous crystal materials with specific physicochemical properties through different construction units. However, due to the intrinsic characteristics of COF materials, such as low crystallinity and slow multi-electron diffusion-controlled proton reduction process, how to synthesize a COF material with high efficiency, high response property to light and significant degradation of organic contaminants remains a challenging scientific problem in this field.
Disclosure of Invention
The invention aims to provide a preparation method of a COF material with a two-dimensional nano porous structure, and the prepared COF material has stronger visible light response performance and photocatalysis performance.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a two-dimensional nano-porous structure Pd-COF material comprises the following steps:
step 1, taking 4, 6-diamino resorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine as raw materials, and preparing an organic framework material COF by adopting a gradient thermal polycondensation method, wherein the method specifically comprises the following steps:
step 1.1: weighing synthetic raw materials of 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine;
step 1.2: stirring the 4, 6-diaminoresorcinol dihydrochloride weighed in the step 1.1 in polyphosphoric acid;
step 1.3: adding the 2,4, 6-tri (4-carboxyphenyl) -1,3, 5-triazine weighed in the step 1.1 into the solution in the step 1.2, reacting by adopting a gradient thermal polycondensation method, and then cooling to room temperature;
step 1.4: washing the product obtained after the reaction in the step 1.3 by using deionized water to remove polyphosphoric acid to neutrality;
step 1.5: soxhlet extracting the product obtained after the reaction in the step 1.4 for 72h by using N, N-dimethylformamide, acetone and deionized water as extracting solution;
step 1.6: freeze-drying the product of the step 1.5 at 0 ℃ for 24h to obtain an organic framework material COF;
step 2.1: weighing Pd (OAC)2Dissolving in a round-bottom flask containing dichloromethane solution;
step 2.2: weighing the two-dimensional porous nano COF material prepared in the step 1, adding the two-dimensional porous nano COF material into the round-bottom flask obtained in the step 2.1, and stirring the two-dimensional porous nano COF material for 24 hours at the room temperature of 25-30 ℃;
step 2.3: centrifuging the product obtained in the step 2.2 to remove supernatant liquid to obtain a reddish brown solid;
step 2.4: washing and purifying the reddish brown solid obtained in the step 2.3 for 20-24 hours by using a Soxhlet extractor and taking dichloromethane as a solvent to obtain a reddish brown powdery solid;
step 2.5: and (3) drying the product obtained in the step 2.4 at the temperature of 80 ℃ for 12h under vacuum to obtain Pd-COF.
Further, the mass ratio of the 4, 6-diaminoresorcinol dihydrochloride to the 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine in the step 1.1 is 1.2: 1-1.5: 1.
Further, the molar volume ratio of the 4, 6-diaminoresorcinol dihydrochloride to the polyphosphoric acid in the step 1.2 is 10-15 mmol/L.
Further, in the step 1.2, the desalting and acid removing process needs to be carried out for 8-10 hours at the temperature of 65-80 ℃ under the protection of nitrogen.
Further, the reaction mixture in the step 1.3 is subjected to a gradient thermal polycondensation method, and is reacted for 6 hours, 12 hours and 12 hours at the temperature of 110-120 ℃, 130-140 ℃, 150-160 ℃ and 170-180 ℃ respectively.
Further, the COF material is mixed with Pd (OAC)2The mass ratio of (A) to (B) is 3:1-5:1, and the dosage of the dispersant dichloromethane is 60-100 mL.
Compared with the prior art, the invention can obtain the following technical effects:
1) the preparation method provided by the invention successfully synthesizes the organic framework material COF by using a simple gradient thermal polycondensation method, the reaction condition is mild, and the synthesis process is simple and easy to realize;
2) compared with the existing 2D COFs material, the covalent bond rigidity in the benzo-bisoxazole group in the COF structure based on the triazine structure is higher, so that the product has good chemical stability, thermal stability and mechanical stability;
3) the structure of the constructed unit of the COF and the complex structure is novel, and the COF and the complex structure show excellent adsorption performance and photocatalytic performance;
4) the preparation method provided by the invention adopts Pd (OAC)2The functional modification is carried out on an organic framework material COF as a Pd source, so that the response capability and the electron transmission capability of the COF material to light can be effectively improved, and the photocatalytic performance of the COF material is further improved;
5) compared with COF, the Pd-COF material with the nano-porous structure prepared by the preparation method provided by the invention has stronger capability of degrading antibiotics by visible light catalysis.
Drawings
FIG. 1 is a preparation process route diagram of a two-dimensional nano-porous Pd-COF material of the invention;
fig. 2 is a fourier infrared spectrum of a COF material prepared by the method of preparing a two-dimensional nanoporous structure COF material of the invention example 1 and using raw materials of 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine;
FIG. 3 is a solid NMR spectrum of the COFs material prepared in example 1 of the preparation method of the two-dimensional nanoporous Pd-COF material of the invention;
FIG. 4 is a scanning electron microscope image of a two-dimensional nano-porous Pd-COF material prepared by the method of example 1;
FIG. 5 is a UV diffuse reflection diagram of a two-dimensional nano-porous Pd-COF material and a Pd-COF complex material prepared in example 1 of the preparation method of the two-dimensional nano-porous Pd-COF material;
FIG. 6 is a diagram showing the catalytic degradation of organic dyes methylene blue and rhodamine B by the COF material and its complex prepared in example 1 of the preparation method of a two-dimensional nanoporous Pd-COF material according to the present invention;
FIG. 7 is a diagram showing the effect of the COF material and the complex thereof prepared in example 1 of the preparation method of the two-dimensional nanoporous Pd-COF material of the invention on photocatalytic degradation of antibiotic sulfadimidine.
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented.
A preparation method of a two-dimensional nano-porous structure Pd-COF material comprises the following steps:
step 1, taking 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine as raw materials, preparing an organic framework material COF by a gradient thermal polycondensation method, as shown in figure 1, specifically:
step 1.1: weighing synthetic raw materials 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, wherein the mass ratio of the 4, 6-diaminoresorcinol dihydrochloride to the 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine is 1.2: 1-1.5: 1.
Step 1.2: stirring the 4, 6-diaminoresorcinol dihydrochloride weighed in the step 1.1 in polyphosphoric acid, wherein the molar volume ratio of the 4, 6-diaminoresorcinol dihydrochloride to the polyphosphoric acid is 10-15 mmol/L, and stirring for 8-10 hours at the temperature of 65-80 ℃ under the protection of nitrogen in a desalting process;
step 1.3: adding the 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine weighed in the step 1.1 into the solution in the step 1.2, reacting by adopting a gradient thermal polycondensation method for 6 hours, 12 hours and 12 hours at the temperature of 110-120 ℃, 130-140 ℃, 150-160 ℃ and 170-180 ℃ respectively, and then cooling to room temperature;
step 1.4: washing the product obtained after the reaction in the step 1.3 by using deionized water to remove polyphosphoric acid to neutrality;
step 1.5: soxhlet extracting the product obtained after the reaction in the step 1.4 for 72h by using N, N-dimethylformamide, acetone and deionized water as extracting solution;
step 1.6: and (3) freeze-drying the product obtained in the step (1.5) at 0 ℃ for 24h to obtain the organic framework material COF.
The specific synthetic route is as follows:
step 2.1: weighing Pd (OAC)2Dissolving in a round-bottom flask containing dichloromethane solution;
step 2.2: weighing the two-dimensional porous nano COF material prepared in the step 1, adding the two-dimensional porous nano COF material into the round-bottom flask obtained in the step 2.1, and stirring the two-dimensional porous nano COF material for 24 hours at the room temperature of 25-30 ℃;
step 2.3: centrifuging the product obtained in the step 2.2 to remove supernatant liquid to obtain a reddish brown solid;
step 2.4: washing and purifying the reddish brown solid obtained in the step 2.3 for 20-24 hours by using a Soxhlet extractor and taking dichloromethane as a solvent to obtain a reddish brown powdery solid;
step 2.5: and (3) drying the product obtained in the step 2.4 at the temperature of 80 ℃ for 12h under vacuum to obtain Pd-COF.
Wherein the COF material is in contact with Pd (OAC)2The mass ratio of (A) to (B) is 4:1, and the dosage of the dispersant dichloromethane is 60～100mL。
Example 1
Step 1: the method is characterized in that 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine are used as raw materials, and an organic framework material COF is prepared by a gradient thermal polycondensation method, and specifically comprises the following steps:
step 1.1: weighing synthetic raw materials 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, wherein the ratio of the amount of the 4, 6-diaminoresorcinol dihydrochloride to the amount of the 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine is 1.2:1, 4, 6-diaminoresorcinol dihydrochloride is 1.7mmol, and the amount of the 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine is 1.13 mmol;
step 1.2: stirring the 4, 6-diaminoresorcinol dihydrochloride weighed in the step 1.1 in polyphosphoric acid at 70 ℃ for 8 hours under the protection of nitrogen, wherein the molar volume ratio of the 4, 6-diaminoresorcinol dihydrochloride to the polyphosphoric acid is 10 mmol/L;
step 1.3: adding the 2,4, 6-tri (4-carboxyphenyl) -1,3, 5-triazine weighed in the step 1.1 into the solution in the step 1.2, reacting for 6 hours, 12 hours and 12 hours at the temperature of 110 ℃, 130 ℃, 150 ℃ and 170 ℃ respectively, and cooling to room temperature;
step 1.4: washing the product obtained after the reaction in the step 1.3 by using deionized water to remove polyphosphoric acid to neutrality;
step 1.5: soxhlet extracting the product obtained after the reaction in the step 1.4 for 72h by using N, N dimethylformamide, acetone and deionized water as extracting solution;
step 1.6: and (3) freeze-drying the product obtained in the step (1.5) at 0 ℃ for 24h to obtain the two-dimensional porous nano COF material.
Step 2: application of Pd (OAC)2Modifying an organic framework material COF as a Pd source to obtain a two-dimensional nano porous structure Pd-COF material, which specifically comprises the following steps:
step 2.1: weighing Pd (OAC)245mg was dissolved in a round bottom flask containing 60ml of dichloromethane solution;
step 2.2: weighing 135mg of the two-dimensional porous nano COF material generated in the step 1, adding the two-dimensional porous nano COF material into the round-bottom flask obtained in the step 2.1, and stirring the two-dimensional porous nano COF material for 24 hours at room temperature of 25 ℃;
step 2.3: centrifuging the product obtained in the step 2.2 to remove supernatant liquid to obtain a reddish brown solid;
step 2.4: washing and purifying the reddish brown solid obtained in the step 2.3 for 20 hours by using a Soxhlet extractor and taking dichloromethane as a solvent to obtain a reddish brown powdery solid;
step 2.5: and (3) drying the product obtained in the step 2.4 at 80 ℃ for 12h under vacuum to obtain the complex Pd-COF.
Fig. 2 is a fourier infrared spectrum of a COF material prepared by the method of preparing a two-dimensional nanoporous Pd-COF material of the present invention, and the raw materials used in the COF material prepared in example 1 are generated with 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine. As can be seen from FIG. 2,4, 6-diaminoresorcinol dihydrochloride is present at 3100-3600 cm-1Shows a broad absorption peak in the wavelength range, belonging to the N-H bond and the phenolic hydroxyl-OH functional group. C ═ O bond and-OH bond in carboxyl group in 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine are at 1692cm due to stretching vibration-1,3138cm-1An absorption peak with a stronger signal exists; an infrared spectrum of the two-dimensional porous nano COF material shows that C ═ O in 2,4, 6-tri (4-carboxyphenyl) -1,3, 5-triazine is 1692cm-1The peak intensity of the characteristic absorption peak is obviously weakened after the polymerization reaction occurs, which shows that the benzobisoxazole structure is generated between the phenolic hydroxyl group and the amino group of the 4, 6-diaminoresorcinol dihydrochloride and the carboxyl group of the triazine structure, and covalent bonds exist among the three groups to generate the target conjugated macrocyclic structure. Besides, the infrared spectrum is 1015cm-1，1096cm-1，1238cm-1Stretching vibration with wavelength of C-N bond; 1262cm-1Is a telescopic vibration of ═ C-O-C, 1628cm-1The data further demonstrate the presence of a benzobisoxazole group between 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine for stretching vibration of the C ═ N bond, demonstrating successful synthesis of the desired product.
FIG. 3 shows a solid NMR spectrum of a two-dimensional nano-porous Pd-COF material prepared in example 1 of the preparation method of the present invention. As can be seen from the spectra, the COF materials show significantly different resonance signals. From the structural analysis, the number of carbon spectra should be 7 theoretically, and actually observed in the spectra, the chemical shifts corresponding to C-1 and C-5 in the rigid benzobisoxazole group generated by the reaction are 170ppm, the chemical shifts corresponding to C-2 and C-4 are 162ppm, C-6 and C-8 respond at the chemical shift of 148ppm, the chemical shifts corresponding to other asymmetric carbon atom C-7 signal peaks are 110ppm, and C-7 is actually observed3A signal peak at 94 ppm; c-9 to C-13 are framework carbon atoms of a benzene ring and are in the same chemical environment, so that a peak with a chemical shift of 139ppm belongs to C-9 to C-13, and in addition, a response signal peak exists at a position with a chemical shift of 129ppm at the terminal carbon C-14 of the benzene ring, which proves that the COFs framework material is successfully synthesized according to the expected design.
Fig. 4 is an electron microscope scanning image of the COF material and its complex prepared in example 1 of the preparation method of a two-dimensional nanoporous Pd-COF material of the invention. As can be seen from fig. 4(a), the external structure of the resultant COF is irregular and the particle size distribution is not uniform. Comparing the electron microscope spectrogram of the COF, the electron microscope of the complex Pd-COF shows that the number of molecules with small particle size and the degree of amorphous form are obviously increased after the complex is added as shown in FIG. 4(b), which shows that part of the Pd-COF ligand is matched with the COF to form the Pd-COF complex.
Fig. 5 is a uv-diffuse reflection diagram of a COF material prepared in example 1 of a preparation method of a two-dimensional nanoporous Pd-COF material according to the present invention. As can be seen from FIG. 5, the synthesized COF and Pd-COF complexes have obvious strong absorption bands at the 400-800nm visible-near infrared band, and the absorption range is obviously widened, which indicates that the COF and the complexes thereof have obviously improved response capability to visible light.
Fig. 6 is an ultraviolet absorption spectrum of a two-dimensional nanoporous Pd-COF material and its complex photocatalytic degradation of methylene blue and rhodamine B, respectively, prepared by the method of preparing a two-dimensional nanoporous Pd-COF material of the invention in example 1. FIG. 6(a) is a spectrum of absorption of methylene blue ultraviolet for COF photocatalytic degradation; FIG. 6(B) is the ultraviolet absorption spectrum of the rhodamine B photocatalytic degradation by COF; FIG. 6(c) is a spectrum of absorption of methylene blue ultraviolet by photocatalytic degradation of COF complex; FIG. 6(d) is the UV absorption spectrum of the photocatalytic degradation of rhodamine by COF complexes. From the figures, it can be clearly observed that when adsorption-desorption reaches equilibrium in a dark cabinet for 30min after adding the COF, the concentration of the organic dye is reduced to a position where the absorption value is close to zero, and therefore, the COF material and the complex thereof which are generated have good adsorption performance and achieve the expected effect.
FIG. 7 shows UV absorption spectra of the two-dimensional nano-porous Pd-COF material and its complex Pd-COF in visible light catalyzed sulfadimidine degradation, respectively, according to the preparation method of the two-dimensional nano-porous Pd-COF material of the present invention, prepared in example 1. FIG. 7(a) is a spectrum of HPCL for COF photocatalytic degradation of sulfadiazine; FIG. 7(b) is the spectrum of Pd-COF photocatalytic degradation sulfadiazine HPCL. The graph shows that COF and COF complexes have good degradation rate on the antibiotic sulfadimethomozine, and compared with COF, the COF complexes have higher degradation rate on the antibiotic under visible light irradiation, and the degradation rate is 96.12%.
Example 2
Step 1: the method is characterized in that 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine are used as raw materials, and an organic framework material COF is prepared by a gradient thermal polycondensation method, and specifically comprises the following steps:
step 1.1: weighing the synthetic raw materials of 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, wherein the molar ratio of the 4, 6-diaminoresorcinol dihydrochloride to the 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine is 1.35: the amount of 1, 4, 6-diaminoresorcinol dihydrochloride substance was 1.9125mmol, and the amount of 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine substance was 1.42 mmol;
step 1.2: stirring the 4, 6-diaminoresorcinol dihydrochloride weighed in the step 1.1 in polyphosphoric acid at 65 ℃ for 9 hours, wherein the molar volume ratio of the 4, 6-diaminoresorcinol dihydrochloride to the polyphosphoric acid is 12 mmol/L;
step 1.3: adding the 2,4, 6-tri (4-carboxyphenyl) -1,3, 5-triazine weighed in the step 1.1 into the solution in the step 1.2, reacting for 6 hours, 12 hours and 12 hours at the temperature of 115 ℃, 135 ℃, 155 ℃ and 175 ℃ respectively, and cooling to room temperature;
step 1.4: washing the product obtained after the reaction in the step 1.3 by using deionized water to remove polyphosphoric acid to neutrality;
step 1.5: soxhlet extracting the product obtained after the reaction in the step 1.4 for 72h by using N, N dimethylformamide, acetone and deionized water as extracting solution;
step 1.6: and (3) freeze-drying the product obtained in the step (1.5) at 0 ℃ for 24h to obtain the two-dimensional porous nano COF material.
Step 2: application of Pd (OAC)2Modifying an organic framework material COF as a Pd source to obtain a two-dimensional nano porous structure Pd-COF material, which specifically comprises the following steps:
step 2.1: weighing Pd (OAC)245mg was dissolved in a round bottom flask containing 80ml of dichloromethane solution;
step 2.2: weighing 180mg of the two-dimensional porous nano COF material generated in the step 1, adding the two-dimensional porous nano COF material into the round-bottom flask obtained in the step 2.1, and stirring the two-dimensional porous nano COF material at room temperature of 28 ℃ for 24 hours;
step 2.3: centrifuging the product obtained in the step 2.2 to remove supernatant liquid to obtain a reddish brown solid;
step 2.4: washing and purifying the reddish brown solid obtained in the step 2.3 for 22 hours by using a Soxhlet extractor and taking dichloromethane as a solvent to obtain a reddish brown powdery solid;
step 2.5: and (3) drying the product obtained in the step 2.4 at 80 ℃ for 12h under vacuum to obtain the complex Pd-COF.
Example 3
Step 1: the method is characterized in that 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine are used as raw materials, and an organic framework material COF is prepared by a gradient thermal polycondensation method, and specifically comprises the following steps:
step 1.1: weighing the synthetic raw materials of 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, wherein the molar ratio of the 4, 6-diaminoresorcinol dihydrochloride to the 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine is 1.5: the amount of 1, 4, 6-diaminoresorcinol dihydrochloride substance was 2.125mmol, and the amount of 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine substance was 1.42 mmol;
step 1.2: stirring the 4, 6-diaminoresorcinol dihydrochloride weighed in the step 1.1 in polyphosphoric acid at the temperature of 80 ℃ for 10 hours under the protection of nitrogen, wherein the molar volume ratio of the 4, 6-diaminoresorcinol dihydrochloride to the polyphosphoric acid is 15 mmol/L;
step 1.3: adding the 2,4, 6-tri (4-carboxyphenyl) -1,3, 5-triazine weighed in the step 1.1 into the solution in the step 1.2, reacting for 6 hours, 12 hours and 12 hours at the temperature of 120 ℃, 140 ℃, 160 ℃ and 180 ℃, respectively, and cooling to room temperature;
step 1.4: washing the product obtained after the reaction in the step 1.3 by using deionized water to remove polyphosphoric acid to neutrality;
step 1.5: soxhlet extracting the product obtained after the reaction in the step 1.4 for 72h by using N, N dimethylformamide, acetone and deionized water as extracting solution;
step 1.6: and (3) freeze-drying the product obtained in the step (1.5) at 0 ℃ for 24h to obtain the two-dimensional porous nano COF material.
Step 2: application of Pd (OAC)2Modifying an organic framework material COF as a Pd source to obtain a two-dimensional nano porous structure Pd-COF material, which specifically comprises the following steps:
step 2.1: weighing Pd (OAC)245mg was dissolved in a round bottom flask containing 100ml of dichloromethane solution;
step 2.2: weighing 225mg of the two-dimensional porous nano COF material generated in the step 1, adding the two-dimensional porous nano COF material into the round-bottom flask obtained in the step 2.1, and stirring the materials at room temperature of 30 ℃ for 24 hours;
step 2.3: centrifuging the product obtained in the step 2.2 to remove supernatant liquid to obtain a reddish brown solid;
step 2.4: washing and purifying the reddish brown solid obtained in the step 2.3 for 24 hours by using a Soxhlet extractor and taking dichloromethane as a solvent to obtain a reddish brown powdery solid;
step 2.5: and (3) drying the product obtained in the step 2.4 at 80 ℃ for 12h under vacuum to obtain the complex Pd-COF.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A preparation method of a two-dimensional nano-porous structure Pd-COF material is characterized by comprising the following steps
The method comprises the following steps:
step 1, taking 4, 6-diamino resorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine as raw materials, and preparing an organic framework material COF by adopting a gradient thermal polycondensation method, wherein the method specifically comprises the following steps:
step 1.1: weighing synthetic raw materials of 4, 6-diaminoresorcinol dihydrochloride and 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine;
step 1.2: stirring the 4, 6-diaminoresorcinol dihydrochloride weighed in the step 1.1 in polyphosphoric acid;
step 1.3: adding the 2,4, 6-tri (4-carboxyphenyl) -1,3, 5-triazine weighed in the step 1.1 into the solution in the step 1.2, reacting by adopting a gradient thermal polycondensation method, and then cooling to room temperature;
step 1.4: washing the product obtained after the reaction in the step 1.3 by using deionized water to remove polyphosphoric acid to neutrality;
step 1.5: soxhlet extracting the product obtained after the reaction in the step 1.4 for 72h by using N, N-dimethylformamide, acetone and deionized water as extracting solution;
step 1.6: freeze-drying the product of the step 1.5 at 0 ℃ for 24h to obtain an organic framework material COF;
step 2, use Pd (OAC)2Modifying an organic framework material COF as a Pd source to obtain a two-dimensional nano porous structure Pd-COF material, which specifically comprises the following steps:
step 2.1: weighing Pd (OAC)2 Dissolving in a round-bottom flask containing dichloromethane solution;
step 2.2: weighing the two-dimensional porous nano COF material prepared in the step 1, adding the two-dimensional porous nano COF material into the round-bottom flask obtained in the step 2.1, and stirring the two-dimensional porous nano COF material for 24 hours at the room temperature of 25-30 ℃;
step 2.3: centrifuging the product obtained in the step 2.2 to remove supernatant liquid to obtain a reddish brown solid;
step 2.4: washing and purifying the reddish brown solid obtained in the step 2.3 for 20-24 hours by using a Soxhlet extractor and taking dichloromethane as a solvent to obtain a reddish brown powdery solid;
step 2.5: and (3) drying the product obtained in the step 2.4 at the temperature of 80 ℃ for 12h under vacuum to obtain Pd-COF.
2. The method for preparing a Pd-COF material with a two-dimensional nano-porous structure according to claim 1, wherein the mass ratio of the 4, 6-diaminoresorcinol dihydrochloride to the 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine in the step 1.1 is 1.2:1 to 1.5: 1.
3. The method for preparing a Pd-COF material with a two-dimensional nano-porous structure according to claim 1, wherein the molar volume ratio of the 4, 6-diaminoresorcinol dihydrochloride to the polyphosphoric acid in step 1.2 is 10-15 mmol/L.
4. The method for preparing a Pd-COF material with a two-dimensional nano-porous structure according to claim 1, wherein the hydrochloric acid removal process in step 1.2 requires stirring at 65-80 ℃ for 8-10 h under the protection of nitrogen.
5. The method for preparing a Pd-COF material with a two-dimensional nano-porous structure according to claim 1, wherein the reaction mixture in step 1.3 is subjected to a gradient thermal polycondensation reaction at a temperature of 110-120 ℃, 130-140 ℃, 150-160 ℃, 170-180 ℃ for 6 hours, 12 hours, and 12 hours, respectively.
6. The method for preparing a Pd-COF material with a two-dimensional nano-porous structure according to claim 1, wherein the COF material is mixed with Pd (OAC)2The mass ratio of (A) to (B) is 3:1-5:1, and the dosage of the dispersant dichloromethane is 60-100 mL.
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| CN110523354A (en) * | 2019-09-06 | 2019-12-03 | 浙江大学 | A kind of preparation method of the microreactor containing solid-carried catalyst |
| CN111848897A (en) * | 2020-07-15 | 2020-10-30 | 上海交通大学 | Preparation method of covalent organic framework material formed by alternately connecting two types of octapole conjugated structural units through carbon-carbon double bonds |
| CN112111069A (en) * | 2020-09-30 | 2020-12-22 | 中国科学院生态环境研究中心 | Preparation method and application of palladium nanoparticle-supported benzothiazole-linked covalent organic framework material |
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| CN106883364A (en) * | 2017-01-23 | 2017-06-23 | 南开大学 | The preparation method of the covalent organic framework material of trace water in detection organic solvent |
| CN110523354A (en) * | 2019-09-06 | 2019-12-03 | 浙江大学 | A kind of preparation method of the microreactor containing solid-carried catalyst |
| CN111848897A (en) * | 2020-07-15 | 2020-10-30 | 上海交通大学 | Preparation method of covalent organic framework material formed by alternately connecting two types of octapole conjugated structural units through carbon-carbon double bonds |
| CN112111069A (en) * | 2020-09-30 | 2020-12-22 | 中国科学院生态环境研究中心 | Preparation method and application of palladium nanoparticle-supported benzothiazole-linked covalent organic framework material |
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